Substitution reactions that employ primary-carbamoyl-protected arylmethanethiols are described. The enantiodetermining step was found to occur in the post-deprotonation step as a dynamic thermodynamic resolution with a chiral bis(oxazoline) ligand. The configurationally labile lithium complexes were trapped with various electrophiles to yield different substitution products in good to excellent yields and enantiomeric excesses. The absolute configurations of the substitution products were determined, and the stereochemical pathway of the substitution reaction was elucidated for different classes of electrophiles. The temperature-dependent epimerization process was monitored by 1H and 6Li NMR spectroscopy.

Lange, H., Bergander, K., Frohlich, R., Kehr, S., Nakamura, S., Shibata, N., et al. (2008). Highly Enantioselective Reactions of Configurationally Labilem Epimeric Diamine Complexes of Lithiated S-Benzyl Thiocarbamates. CHEMISTRY - AN ASIAN JOURNAL, 3(1), 88-101 [10.1002/asia.200700262].

Highly Enantioselective Reactions of Configurationally Labilem Epimeric Diamine Complexes of Lithiated S-Benzyl Thiocarbamates

Lange, H;
2008

Abstract

Substitution reactions that employ primary-carbamoyl-protected arylmethanethiols are described. The enantiodetermining step was found to occur in the post-deprotonation step as a dynamic thermodynamic resolution with a chiral bis(oxazoline) ligand. The configurationally labile lithium complexes were trapped with various electrophiles to yield different substitution products in good to excellent yields and enantiomeric excesses. The absolute configurations of the substitution products were determined, and the stereochemical pathway of the substitution reaction was elucidated for different classes of electrophiles. The temperature-dependent epimerization process was monitored by 1H and 6Li NMR spectroscopy.
Articolo in rivista - Articolo scientifico
asymmetric synthesis, bis(oxazoline) ligands, carbanions, dynamic thermodynamic resolution, lithium
English
2008
3
1
88
101
reserved
Lange, H., Bergander, K., Frohlich, R., Kehr, S., Nakamura, S., Shibata, N., et al. (2008). Highly Enantioselective Reactions of Configurationally Labilem Epimeric Diamine Complexes of Lithiated S-Benzyl Thiocarbamates. CHEMISTRY - AN ASIAN JOURNAL, 3(1), 88-101 [10.1002/asia.200700262].
File in questo prodotto:
File Dimensione Formato  
Lange et al. Benzylthiocarbamates_Chem. Asian J. 2008, 3, 88-101.pdf

Solo gestori archivio

Dimensione 619.26 kB
Formato Adobe PDF
619.26 kB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/318849
Citazioni
  • Scopus 19
  • ???jsp.display-item.citation.isi??? 14
Social impact